Process of producing vat dyestuffs of the perylene series and the products obtainable thereby



Patented Sept. 1, 1 925. I, i 1

UNITED STATES 1,551,349 a PATENT OFFICE.

KARL SCHIBIAOEIB AND WILKILI :acm'r, OI HOGEST -ON-THE-HAIN, GERIAHY;

ABSIGNOBS 'TO V HISTEBLUCIUB t BBU'NING, OF BOOKST- ON-THE-IAIN, GEBIANY, A CORPORATION 01 GERMANY.

rnocnss or rnonncmo' va'r numerous or ran rnaxminn-ssams AND 'rnnrnonoc'rs onramanm: manner.

10 ihrlwing.

To all whom may concern:

Be it known that we, KARL SCHIRMACHER and WILHELM Eonnn'r, citizens ofGermany,

residing at Hochst-on-the-Main, Germany,

5 have invented certain new and useful Imdyestuffs of the peryleneseries are obtained for instance aluminium chloride, zinc chlobytreating in the heat the oxidation products of vat-dyestuffs havingperylene-structure with acid condensing agents, such as ride etc. and byalkylatin the thus formed new reaction products. he chemicalconstitution of these new dyestuffs. is unknown hitherto; they aredistinguished by pure beautiful tints and. very good fastness prop- 26-dibenzat rone obtainable according to Ex-.

erties.

The following examples illustrate our invention: y

1. 10 arts of the oxidation product of ample 20f United States PatentNo. 1,093,-

427 are heated while stirring with parts 4 of zinc chloride free fromwater to 310-320 C. After termination of the reaction the so cold fusionis made into pieces, boiled u with water, then separated and washed:

. The paste still in a molst state is then heated with 300 soda and 5parts of -toluene-'sulfonic-acid- 86 methylesterto 165-1 0 C. until thedeepblue coloration of the solution no longer increases which is thecase after about 2 hours. The solution is filtered by suction while hot.The reaction productso arates on cooling 40 in blue violet crystals wich possess airincotton violet tints; w

tense metallic lustre when in a dry state and dissolve in concentratedsulfuric acid with a claret-red hue.

The new dyestufi dyles from the violet vat a clear blue is obtained. A

, 2. If instead of the oxidation roduct of dibenzanthrone used accordingto the oxidation product of dimethyl iben- 6 zanthrone is employed andthe operations carried out as stated in'Exam 1e 1, a dye stuff isobtained p "n simi arproperties as those indicated in xample 1. The

Annal'en 394, page 148).' A

parts of the oxidation roduct of enesulfonie-acid-alkylester theremaiigfalso be agents such as for instance dialkyls fate. arts ofnitrobenzene, 15 parts of lenenucleusfwith metallic chlorideseapable enexposed to the air;

1 agents in the heat and methylating the ob xam le 1,

Applleation flled April 27, was. Serial no. cases.

diincthylbenzanthnone canbe prepared by fusln with caustic potash at220.225 C. the

7 -met yl-1.9-benzanthrone of the melting point 158159 C. obtained byScholl by condensing para-toluic acid chloride with naphthalene andsubsequently closing the ring by heating with aluminium chloride "(see3. 10 dibenzanthrone obtainable accor ing to Ex-. ample 2 ofUnitedStates Patent N 0. 1,093;- 427 are heated to 310320 C. with 100 parts ofaluminium chloride, while stirring. The

product of the reaction is boiled'up with diluted hydrochloric acid,filtered by suction washed until neutral and dricd. product isthenheated to slight boiling for 3 hours with 25'-parts of calcined soda and25 parts of p-toluenesulfoniceacid-ethylester in 350 parts ofnitrobenzene,

The further operations are carried out as indicated in Example 1; Thedyestuffs-thus 75 obtained. forms a bluish-violet vat dyeing cotton alsoa bluish-violet tint, which when gilrposed to the air, changes to aclear steel-' ue. Instead of nitrobenzene there may be used othersolvents of high boiling point, such as trichlorobenzene etc'." Insteadof para-toluused with t e same result other a lating We claim-:- 1Process of producing vat-dyestufis which consists in treating theoxidation products of vat-dyestuffs containing a peryof acting asdehydrating or condensing agents in the heat and a tained 'pmducts.

2. Process of producing vat-dyestufis which consists: in treating theoxidation products of vat-dyestuffs containing a perylene nucleus withmetallic chlorides capable of acting as dehydrating or condensingchloride capable of acting as a dehydrating I mcondensmg agent andalkylating the obtrained product.

The

ylating the ob- 4:. Process of producing vat-dyestuffs which consists intreating an oxidation product of a dibenzanthrone with a metallicchloride capable of acting as a dehydrating or condensing agent in theheat and methylating the obtained product.

5. As new products, the vat-dyestuffs, substantially-identical with theproducts obtainable by treating the oxidation products of vat-dyestuffscontaining a perylene nucleus with metallic chlorides capable of actingas dehydrating or condensing agents in the heat and'alkylating theobtained products.

6. As new products, the vat-dyestuffs, substantially identical with theproducts obtainable by treating the oxidation product of. adibenzanthrone with metallic chlorides capable of acting as dehydratingor condensing agents and alkylating the obtained products, being violetpowders, soluble in concentrated sulfuric acid with a violet to redcolor, difiiculty soluble in solvents of a high boiling point, formingavat. of a bluishviolet color from which cotton is dyed blue tints.

7. As new products, mono-alkyloxydibenzanthrones, substantiallyidentical with the dyestuffs obtainable by treating the oxidaboilingpoint, forming a vatof a bluishviolet color from which cotton is dyedblue tints.

8. As a new product, a monomethoxydibenzanthrone, substantiallyidentical with the dyestufl obtainable by treating the oxidation productof a dibenzanthrone with metallic chlorides capable of acting :asdehydrating or condensing agents and methylating the obtained product,being soluble in concentrated sulfuric acid with a claret-red color,forming a bluishvio1et vat from which cotton is dyed steel-blue tints.

' In testimony whereof, we aflix our signatures.

KARL SCHIRMAOHER. WILHELM ECKERT,

